Cool water laundering process

ABSTRACT

A process for laundering fabrics in 60* F.-90* F. Water containing .05-.5 percent of a detergent composition containing 4-35 percent of specific zwitterionic detergents and 8-90 percent of detergency builders which complex the calcium and magnesium ions in hard water.

United States Patent [72] Inventors Francis L.D1ehl Continuation-impartof application Ser. No.

581,720, Sept. 26, 1966, now abandoned which is a continuation-impart ofapplication Ser. No. 413,948, Nov. 25,

v 1964, now abandoned which is a continuation-impart of application Ser.No. 163,041, Dec. 29, 1961, now abandoned. The portion of the term ofthe patent subsequent to Nov. 10, 1987. has been disclaimed.

[54] COOL WATER LAUNDERING PROCESS 5 Claims, No Drawings [52] U.S.CI8/137, 252/137,252/151, 252/152, 252/355,260/50l [51] 1lnt.Cl D061 [50]Field oISearch 252/137, 152. 151, 355', 8/137; 260/50 [56] ReierencesCited UNITED STATES PATENTS 2,129,264 9/1938 Downing et a1 252/152 UX2,702,278 2/1955 Cuperctal. 252/152UX 2,739,942 /1961 Drew et a1.252/138 X 3,213,030 10/1955 Diehl 252/152 FOREIGN PATENTS 1,018,42110/1952 Germany 252/161 1.051.439 211959 Germany 252/152 751,273 7/1956Great Britain 252/137 Primary Examiner Mayer Weinblatt Attorneys-RichardC. Witte, Thomas H. OFlaherty and Robert B. Aylor 7 calcium andmagnesium ions in hard water.

COOL WATER LAUNDERING PROCESS This application is a continuation-in-partof our copending application, Ser. No. 58l,720, filed Sept. 26, 1966,entitled LAUNDERING PROCESS AND DETERGENT COMPOSI- TION THEREFOR, Nowabandoned which was in turn a continuation-in-part of our copendingapplication, Ser. No. 413,948, filed Nov. 25, 1964, entitled LAUNDERINGPROCESS AND DETERGENT COMPOSITION THEREFOR, Now abandoned which was inturn, a continuation-in-part of our earlier field application, Ser. No.163,041, filed Dec. 29, 1961. entitled LAUNDERING PROCESS AND DETERGENTCOMPOSITION THEREFOR, now abandoned.

The present invention relates to the laundering of textile fabrics incool aqueous media employing a composition containing a specific type ofsynthetic detergent compound. More particularly, it relates to a processof, and product for, laundering fabrics in cool water using productscontaining specific sulfo betaine (sultaine) detergent compounds ashereinafter more fully described.

At the present time the synthetic detergent washing compounds used inlaundering clothes and other textile fabrics are utilized in home andcommercial operations at water temperatures ranging from 1 l-l50 F.,with the usual washing temperature being at a median of about 120 to 130F. It is within this temperature range that the most effective washingaction is achieved for the common laundry fabrics such as cottons,woolens, and synthetic fabrics, using the conventional detergentmaterials.

However, it is well known that some fabrics have a pronounced tendencyto shrink, wrinkle, or draw up when washed in water at temperaturesranging from 1l0-l50 F. Such fabrics are the new wash-wear materialslike Dacron, Creslan, resin treated cotton, cloth made from Kodelpolyester fibers, and several other additional ones. It is also wellknown that sweaters, blankets, and other articles made from natural woolshrink considerably when washed at the normal temperatures. Theshrinkage not only alters the size of the article but also changes thecharacteristic and feel of it, making it less soft and pleasant to thetouch. Because of these facts, these fabrics are washed in lukewarm orcool water where shrinkage and drawing up is kept at a minimal level.

Below the normal washing temperature range of 110 to 150 F., theefficiency of the commonly used detergent compositions such as thosecontaining sodium dodecyl benzene sulfonate, the dodecyl group beingderived from tetrapropylene, (currently the most commonly used activeingredient), higher alkyl sulfates, sulfated and sulfonated amides andamines as the active detergent compound, is reduced considerably. Insome instances, sudsing ability of such detergent compounds in coolwaters also reduced, necessitating the addition of organic enhancingagents to the detergent composition to increase sudsing; whitenessmaintenance is poor and in general, conventional detergent compoundssimply have a marked lower level of detergency performance at lowertemperatures. Therefore, it can readily be seen that when fabrics arewashed in cool water to avoid shrinkage and other problems, thehousewife will usually pour more detergent composition than normal intothe washing solution in an attempt to achieve the same cleaning level aswould be obtained at normal temperatures. This is both wasteful anduneconomical because there is little indication that the same cleaninglevel could be achieved in cool water by the addition of excessdetergent composition as is obtained in washing clothes at the normaltemperatures using normal amounts of detergent composition in thesolution.

Additionally, in many of the economically less well developed areas ofthe world, particularly the South American and Asian countries, clotheswashing and other laundry tasks are commonly performed at temperaturesbelow 100 F. using comparatively crude methods. At these cool watertemperatures, as previously mentioned, the most commonly used syntheticdetergent compositions have only moderate detergency power, and as aresult it tends to promote wastefulness for the reason that excessdetergent material is then used in an effort to achieve higher cleaningperformance.

It can be appreciated too that considerable savings in fuel bills wouldbe realized over a period of time if an effective way were to be foundto wash clothes in cool water because it takes considerably less fuel toheat water to a temperature of about F. than it does to heat it to thehigher temperatures at which clothes are normally washed.

With the foregoing considerations in mind, it is an object of thepresent invention to provide a process nd a product for washing fabricsusing a detergent composition that will clean as efficiently in coolwater as conventional compositions do at normal washing temperatures.The term "cool water" as used herein is defined to mean water which isat a temperature ranging from about 40 F. to about F.

It is a further object of the present invention to provide a process anda product for washing fabrics which will minimize the amount ofshrinking, drawing up, or wrinkling of fabrics that occurs under normalwashing conditions.

Other objects and advantages of the invention will be apparent duringthe course of the ensuing description.

It has been found that these objects can be accomplished by a washingprocess comprising the step of washing fabrics in cool aqueous solution,the solution containing a detergent composition consisting essentiallyof a builder salt and a quaternary ammonium compound having the generalformula wherein R, represents an alkyl radical having from about i 2 toabout 18 carbon atoms, R and R are each selected from the groupconsisting of methyl, ethyl, propyl, butyl, and ethanol radicals, R isan alkylene chain having from I to about 3 carbon atoms, and X isselected from "the group consisting of hydrogen and hydroxyl radicals,wherein the sum of the R,, R and R radicals total 14-20 carbon atoms.Branched chain alkylene groups, e.g.,

can be substituted for the group in the above formula.

Compounds which conform to the above general formula are characterizedby the presence of both positive and negative charges which areinternally neutralized (i.e., zwitterionic). Where R is 16 carbon atoms,R and R are methyl groups, and R, is an ethylene group, the chemicalname is 3- N,N-dimethyl-NhexadecylammonioI) propanel -sulfonate. Where Ris 16 carbon atoms, R and R are methyl groups and R is an ethylene chainwith a hydroxy radical attached to the second carbon atom, the compoundcan be described as 3- (N,N-dimethyl-N-hexadecylammonio))-2-hydroxypropanel sulfonate. These compounds are commonly calledsultaines or sulfo betaines and can be prepared in the manner disclosedin US. Pat. No. 2,l 29,264 and German Pat. No. l,0l8,42l.

The most preferred compounds of this invention are the ones which havebeen shown to have cleaning effectiveness at 80 F. which is equivalentto or greater than that exhibited by sodiumtetrapropylenebenzenesulfonate at F. These compounds are the sultainedetergents selected from the group consisting of l. 3-(N,N-bibutyl-N-alkylammoniio)propanel -sulfonates wherein the alkyl groupcontains from about 12 to about 16 carbon atoms;

2. 3-( N ,N-dibutylN-alkylammonio)propancl -sulfonates wherein the alkylgroup contains about 12 carbon atoms;

3. 3-(N,N-diemthyl-N-alkylammonio)-2-hydroxypropanel-sulfonates whereinthe alkyl group contains from about 12 to about [6 carbon atoms;

4. 3-( N,N-dimethyl-N-alkylammonio)- l ,1,3-trimethylpropanc-l-sulfonate wherein the alkyl group contains about12 carbon atoms;

5. 2-(N,N-dimethyl-N-alkyl)ethane-l-sulfonate wherein the alkyl iscoconut oil-derived; and

6. Mixtures thereof.

Within the above preferred compounds there are several compounds whichare particularly outstanding. For example, compound 1 is most effectiveat cleaning fabrics in cool water when the alkyl group contains 16carbon atoms. Also, when in compound 3, the alkyl group contains 12carbon atoms or is a mixture of alkyl groups such as those derived fromcoconut oil (or an equivalent synthetic source) and containing l2, l4,and 16 carbon atoms, the sultaines are especially effective at cleaningfabrics in cool water. Compounds 2, 4 and 5, as disclosed above, arevery effective, as hereinafter demonstrated.

The sum of the carbon chain lengths of the R,, R and R,, componentgroups of the compounds have been found to be a critical factor inachieving good detergency performance. The carbons in the R,, R,,. andR,, groups must total 14-20 with the R, group being not less than l2 normore than 18 carbon atoms because it has surprisingly been found thatthe sultaine compounds having such chain length combinations have asignificantly greater cool water cleaning performance and whitenessmaintenance than do those sultaine compounds not so limited and whichfall outside the range of the invention.

Convenient sources of the R, component are coconut fatty alcohols.(These normally consist of a mixture of chain lengths, beingapproximately 0.7 percent C,,, 8.9 percent C,,, 6.8 percent C,,,, 47.2percent C 18.6 percent C 8.3 percent C and 9.5 percent C,,.,.) andtallow fatty alcohols. (These normally consist of a mixture of chainlengths, being approximately 66 percent C,,,, 30 percent C,,,, and 4percent C and others.) R, can also be derived from other naturallyoccurring substances and can also be derived from petroleum fractions,e.g., by polymerizing alkylenes or cracking waxes to form the properchain lengths, e.g., in the form of olefins. The method of deriving thealkyl chains is immaterial. The alkyl chains can be unsaturated.

Another convenient source of the R, component of the sultaine where R,is to average about 12 carbon atoms is that obtained from the middle cutof distilled coconut fatty alcohol which also consists of a mixture ofvarious chain lengths, being approximately 2 percent C 66 percent C 23percent C and 9 percent C Specific sultaine compounds within the generalformula set forth above useful in this invention are: 3-(N,N-diemthyl-N-hexadecylammonio)-2-hydroxypropanel 3-( N,N-diemthyl-N-alkylammonio)-2-hydrosypropane-l-sulfonate; the alkyl group derived fromtallow fatty alcohol; 3-(N,N-diethyl-N-hexadecylammonio)-2-hydroxypropanel -sulfonate; 3-( N,N-diethyl-N-hexadecylammonio )propanel -sulfonate; 3-( N,N-diethyl-N-tetradecylammonio)propane-Lsulfonate; 3-(N,N-diethyl-N-tetradecylammonio)-2-hydroxypropane-l-sul fonate;3-N,N-dimcthyl-N,N-tetradecylammonio)-2-hydroxypropane-l-sulfonate, thealkyl group being derived from the middle cut of coconut fatty alcohol;3-(N,N-dimethyl-N-octadecylammonio )-2-hydroxypropanel -sulfonate; 3-(N2- hydroxyethyl-N-methyl-Ntetradecylammino )propane- 1 -sulfonate;3-(N-2-hydroxyethyl-N-methyl-N-tetradecylammonio)butane-butane-l-sulfonate;butane-l-sulfonate; 3-(N.N,-dimethyl-N-dodecylammonio)-propane-l-sulfonate; 4-(N-Z-hydroxyethyl-N-methy )-N-tetra-decylammonio )-3-hydroxybutancJ-sulfonate; and 3-[N,Nbis(2-hydroxyethyl), N-tetradecylammonio lpropanel -sulfonate. Specific reference to the abovecompounds is given only for the purpose of illustration and it will beappreciated that many other similar variations may be used in thisinvention so long as the important R,, R R and R, requirements describedabove are observed.

In this invention the active sultaine detergent compound is incorporatedinto the total detergent composition at an active to builder ratioranging from about 5:l to 1:25, desirably at levels ranging from about 4percent to about 35 percent of the composition. Below a level of about 4percent it has been found that the total amount of composition needed inthe wash solution to utilize the detergent compounds described in thepresent invention to full advantage is inconveniently large. (A 4percent usage level (liquid composition) is approximately equal to aconcentration of detergent compound in solution of about 0.0088 percent,assuming conventional amounts of water and composition are being used);preferably not more than about 35 percent of the sultaine is used in thedetergent composition because the best results are achieved when theremaining 65 percent of the detergent composition comprises substantialamounts of builder salts together with whatever other valuabledetergency aids (e.g., antiredeposition agents such ascarboxymethylcellulose or anticorrosive agents such as sodium silicate)are desired.

An essential component of the composition utilized in this invention isa water-soluble inorganic alkaline builder salt or an organic alkalinesequestrant builder salt. Suitable inorganic builders include sodium andpotassium tripolyphosphates and pyrophosphates. Examples of organicalkaline sequestrant builder salts are l alkali metal aminopolycarboxylates [e.g., sodium and potassium ethylenediamine-tetraacetates, N-(2- hydroxyethyl)-ethylene diamine triacetates,nitrilotriacetates, and N-(2-hydroxyethyl)-nitrilo diacetates]; 2 alkalimetal salts of phytic acid e.g., sodium and potassium phytatessee U.S.Pat. No. 2,739,942); 3 water soluble salts of methylene disphosphonicacid e.g., trisodium and tripotassium methylene diphosphonate and theother diphosphonate salts described in the copending application ofFrancis L. Diehl, Ser. No. 266,025, filed Mar. 18, 1963, now U.S. Pat.No. 3,213,030 4 water soluble salts of substituted methylenediphosphonic acids e.g., trisodium and tripotassium ethylidene,isopropylidene, benzylmethylidene, and halomethylidene diphosphonatesand the other substituted methylene diphosphonates disclosed in thecopending application of Clarence H. Roy, Ser. No. 266,055, filed Mar.18, i963 now U.S. Pat. No. 3,422,02l ,and 5 mixtures thereof.

Any of the above builders can be used in the form of their ammonium,triethanolammonium,dicthanolammonium, monoethanolammonium, sodium, andpotassium salts, and mixtures thereof.

These alkaline compounds serve to complex the calcium and magnesium ionspresent in hard water and they also serve to increase the level ofdetergency obtainable with synthetic detergent compounds. Othercompounds such as sodium or potassium orthophosphate, sodium, silicate,sodium carbonate and sodium borate can be added to increase detergencyalthough they do not complex the calcium and magnesium ions present inhard water.

The above designated builders are employed at a ratio of builder todetergent compound of from about l:5 to about 25: l desirably at levelsfrom about 8 percent to about percent by weight of the totalcomposition. The balance of the composition, in addition to thedetergent compound as mentioned previously, can consist of water, sodiumsulfate, and other additives valuable as detergency aids, as, forexample, anti-redeposition agents, anticorrosion agents, perfume and thelike.

it is believed that the sultaine detergent compounds of this invention,when used alone in a composition without the presence of builders andother clectroyltes, are not good cool water detergents because they donot possess the essential solubility characteristics for such use. Thebuilders are added, not only to improve detergency as is ordinarily thecase with most synthetic detergent compounds but also to act as anelectrolyte in reducing the Krafft point of the sultaine compounds ofthis invention to such an extent that they are soluble in cool water andare capable of acting as outstanding detergent compounds. lf a nonbuiltcomposition is desired, then sufficient inorganic or organicelectrolytes must be added to insure solubility of the sultaines inaqueous solution. Suitable electrolytes may be, for example, NaCll,liCll, Na SO,,, and NAT.

The discovery that the sultaine-type compounds described in thisinvention show exceptional cool water detergency was unpredictable inview of the fact that there is no published theory or backgroundinformation on the mechanics of cool water detergency. Moreover, thoseconventional compounds such as dodecyl benzene sulfonate which are goodhot water (130 F.-l40 1F.) detergent compounds show a minimum ofactivity in cool water. From the published literature one would be ledto assume that these compounds of the invention would be, comparativelyspeaking, as poor as any other conventional detergent compounds whenused in cool water; however, as has been discovered, the sultainesdescribed in the present invention are far more effective in cool waterthan many of the commonly used commercially available detergentcompounds are in hot water. it can therefore be seen that the structureof a given detergent compound effective in hot water has little or norelation to the effectiveness of such compounds in cool water.

It has also surprisingly been found that the compounds used in thisinvention exhibit good detergent properties when used in wash water atvery low concentrations. For example, it was found that the cleaningability of the preferred 3-(N,N- dimethyl'N-hexadecylammonio) propane-l-sulfonate in the presence of 0.06 percent sodium tripolyphosphatebuilder in solution decreases only slightly as the concentration of thedetergent compound in solution is substantially decreased from 0.03percent to 0.01 percent. Other common detergent compounds lose theireffectiveness at such low concentrations. The concentration of adetergent compound in solution usually employed is conventionalhousehold washing situations ranges from about 0.45 percent for granulesto 0.026 percent for liquids.

It has also been found that the maximum detergency of the compositionsof this invention is achieved when the pH of the washing solution, atcool water temperatures, is within a range of about 8 to about 12 withthe preferred pl-l being 10.5 to 1 L5. Using normal amounts of water forwashing, a pill of l l of the solution can be obtained by incorporatinginto the compositions of this invention a normal amount of silicate,i.e., up to 8 percent by weight. The silicate acts as a buffer and alsoas a corrosion inhibitor. The washing step in the laundering method ofthis invention can be practiced in a number of different, butconventional, ways so long as the essential detergent composition isused. Preferably the step of washing is followed by rinsing and dryingthe fabrics. For example,-the washing solution to be used in the washingstep can be prepared by adding the detergent composition of thisinvention to a tub or automatic washer or any other container whichcontacts cool water at a temperature ranging from about 40 F. to about100 F. The detergent product concentration in solution can range fromabout 0.05 percent to 0.50 percent by total weight, and should be addedin sufficient amount to provide a sultaine detergent compoundconcentration of at least 0.005 percent.

The sultaine detergent compound concentration can be as high as about0.175 percent based upon the use of a 0.5 percent concentration of adetergent composition containing 35 percent of said sultaine detergentcompound. The detergency builder is present in the washing solution inan amount from about 0.004 percent to about 0.45 percent, these figurescorresponding respectively to 0.05 percent of a detergent compositioncontaining 8 percent detergency builder and 0.5 percent of a detergentcomposition containing 90 percent detergent builder. The fabrics can beadded to the container or washer before or after the washing solution isadded. As is usual in a washing step, the fabrics are then agitated inthe detergent solution for varying periods of time, but sufficient toobtain the desired amount of cleaning. With an automatic agitator typewasher, it has been found that good cleaning can be achieved using awashing cycle which ranges from 8 to 15 minutes.

After the desired level of cleaning is achieved in the washing step, thewashing liquor is then drained off or the fabrics are separated from theliquor and thereafter the fabrics are rinsed in substantially purewater. The fabrics can be rinsed as many times as desirable in order toinsure that all of the washing liquor an other undissolved material isseparated from them. Using an automatic washer, it has been found thatsix spray rinses and one deep rinse is usually sufficient for thispurpose. Between and after rinsing steps, the bulk of the rinse water isusually drawn from, or spun out of the fabrics. After rinsing thefabrics can be dried by conventional means, using a machine dryer orsimply hanging them on a line. Although rinsing and drying are usual anddesirable steps, the important advantage of the invention is achieved inthe washing step.

in the following described examples there will be mentioned threedifferent methods of testing the effectiveness of the detergentcompositions used. These tests will be described herein, and are termed,respectively, the Cloth Swatch Test, the White Shirt Detergency Test,and the Regular Wash and Wear Test.

CLOTH SWATCH TEST in a cloth swatch test the detergency effectiveness ofthe sultaine compounds of this invention were determined by washingnaturally soiled cloth (desized print cloth) for l0 minutes in anaqueous solution of a. detergent composition containing the sultainecompound to be tested and a builder (0.03 percent detergent compoundconcentration and 0.06 percent builder concentration in the washsolution at a pH of IO, water at 7 grains per gallon hardness at F. orl40 F.). No fluorescers, bleaches, or antiredeposition agents were used.After washing, rinsing and drying the percent oflipid soil removed fromthe swatch during the washing process was calculated. The percentage ofsoil removed by the sultaine test composition was then compared with thepercentage of lipid soil removed by washing with a known standard(sodium tetrapropylene benzene sulfonate) and in that way the relativeeffectiveness of the compound was determined. A Tergotometer was usedfor the washing operation. (Tergotometer testing is described inDetergency Evaluation and Testing", by J. C. Harris, lntersciencePublishers, Inc. 1954) page 60.)

WHITE SHIRT DETERGENCY TEST In addition to the Cloth Swatch Testdescribed above, the detergency of the sultaine compounds utilized incompositions of this invention was evaluated by washing naturally soiledwhite dress shirts. Shirts are worn by male subjects under ordinaryconditions for two normal working days. The degree to which thedetergent composition containing a detergent compound to be testedcleans the collars and cuffs of the soiled shirts, relative to thecleaning degree of a similar composition containing a standard detergentcompound is considered a measure of the detergency effectiveness of thetest compound.

The washing solution used in the test contains 0.03 percent organicsurface active agent and 0.06 percent sodium tripolyphosphate. (Nofluorescers, bleaches, or antiredeposition agents were used.) The pH ofthe washing solution is 10 and water of 7 grains per gallon hardness isused. A conventional agitator type washer is used. The detergentcompound in the standard detergent composition was sodium tetrapropylenebenzene sulfonate, the most commonly used organic detergent compound inheavy duty laundry detergent compositions. The test detergentcomposition contains the detergent compound to be tested, i.e., comparedwith the standard composition.

WASH-WEAR TEST The standard Wash-wear test mentioned in the examples isconducted as follows:

White dress shirts, cotton T-shirts and other fabrics are distributedamong various male individuals and each shirt and T- shirt is worn forone normal working day under uniform conditions. The soiled shirts andfabrics are then washed in an automatic agitatingntype washer, for aperiod of minutes, with detergent solutions at 80 F. temperature. Afterwashing the clothes are rinsed (six spray rinses and one deep rinse) andthen dried. The water has a hardness of 7 grains per gallon and thedetergent composition concentration in solution is (H5 percent. (Nofluorescers or bleaches are used.) Direct comparisons are made by apanel of 3 skilled graders between pairs of shirts and fabrics worn andsoiled by the same in dividual. The shirts and fabrics are graded on thedegree of cleanness and whiteness maintenance obtained, payingparticular attention to the collars and cuffs. The relative cleaningeffectiveness ofeach detergent composition is graded on a raw scoreunder simulated U.V.-free light and simulated north daylight, averaged,and then translated onto a 1-10 scale wherein on the scale 1 is filthy,5 is acceptable, and I0 is clean, with the remaining numbersrepresenting intermediate values of these conditions.

their detergent power.

EXAMPLE I.

The following test was conducted to illustrate the cleaning efficacy ofa detergent composition containing the preferred sultaine compound ofthe invention at cool water temperatures as compared to compositionscontaining other commonly used commercially available syntheticdetergent com pounds. The cleaning grade of these detergent compoundsdescribed hereafter was established by conducting a standardizedWash-wear test as previously described. In this example the detergencyeffectiveness ofthe sultaine compounds of this invention in cool water(80 F.) is determined by a comparison test in which the sultainecompounds and several well known and commonly used hot water detergentcompounds are substituted for the active compound in a commercialdetergent formulation which has excellent detergent power (in hot water)and the results are graded on a comparative basis for efficacy incleaning. The standardized commercial detergent composition is:

percent detergent compound 50 percent sodium tripolyphosphate 6 percentsilicates 1:2.45 ratio of Na OzSiO 0.4 percent sodiumcarboxymethylcellulose 23 percent l la SO 3.6 percent water andmiscellaneous Cleaning Grade Lt) dilTerence is statistically significantDetergent Compound (active ingredient A. 3-(N,N-dimethyl-N-hexadecylammonio propane-l-sulhonate l0.() B. Condensation product of tetraropylene benzene and ll moles of ethylene oxide 6.95

C. Sodium tallow alkyl sulfate 5.47

D. Sodium tetrapropylene benzene sulfonatc 3.87 E. Potassium coconut oilsoap 0.33

The alkyl chain length distribution of tallow alkyl sulfate isapproximately 66 percent C1, percent Cu, and 4 percent other.

It can be seen that the cool water cleaning efficiency of the sultainecompound contained in a standard composition is pound to be superior tothe other commercial compositions overall cleaning effectiveness at lOO"F. yet as indicated in l ample l above, the sultaine detergentcomposition is market superior to a composition containing sodiumtetrapropyle benzene sulfonate at F.

A White Shirt Detergency Test, previously described, \I conducted usingseveral commercially available detergt compounds in a formulation(containing the detergent co pound to be tested and a builder) incomparison with the tergent compounds utilized in this invention. Thewashi solution contained 0.03 percent detergent compound a 0.06 percentsodium tripolyphosphate. (No fluoresce blcaches or antiredepositionagents were used.) The washi solution had a pH of 10 and the water was 7grains per gall hardness. The detergent compounds used in this test were(N,N-dimethyl, N-hexadecylammonio)propane-l-sulfonate(N,N-dimethyl,N-hexadecylammonio)2-hydroxypropane-lsulfonate, (two ofthe preferred compounds of this invention dimethyldodecylamine oxide,sodium tetrapropylene benze sulfonate, and sodium tallow alkyl sulfate.Under the test cc ditions, the detergency effectiveness of3-(N,N,-diemthylhexadeylammonio) propane-l-sulfonate and 3-(N,diemthyl-N-hexadecylammonio)-2-hydroxypropane-l-sulfonate in wash waterof 80 F. was quite superior to the dett gency effectiveness ofdimethyldodecylamine oxide at 80 and tetrapropylene benzene sulfonate atF., and a greatly superior to the detergency efi'ectiveness of sodium tlow alkyl sulfate and sodium tetrapropylene benzene sulfonz at 80 F. Ifthe pH of the washing solution at 80 F. l Hequivalent to the hydroxylion concentration in solution pH =l0 at 140 F). the margin ofsuperiority of the sultai compounds is increased.

Similar comparative results are obtained if, in the Wh Shirt DetergencyTest, an organic alkaline sequestrant builc salt, sodium ethylenediamine tetraacetate or potassit nitriloacetate, is used instead ofthesodium tripolyphosphatt EXAMPLE ll. Here a Cloth Swatch Test, previouslydescribed, was conducted under the following conditions: water at atemperature of 80 F. or l40 F. and 7 grains per gallon hardness, 0.03percent detergent compound and 0.0 percent sodium tripolyphosphatebuilder concentration in tl washing solution (NO fluorescers, bleaches,or antiredeposition agents were used.) The detergent washing solutionhad a pH of IO.

Lipid Tom; removal, l att [)vtvrgont agent percent A. 3-t I,Nxlimt-tliylN -lioxadecylammouio) -2- liydroxypropauc-l-sulfouatv 66. 2 B. Sodiumtallow alkyl sulfate 66.0 Sodium tvtrapropylvuv Iu-nzcuu sultouatc. 6-1.I) l). 3- (N,N -dimethyl -N -hvxudecylammouio) propaue-l-Sulfouatc 61!.5| E. Sodium tallow alkyl sulfntt- 56. .I F. (undonsatiou product oftallow alcohol and 17 molt-s vthylouo oxide 5t .5 (i. 3- l I.N-tllllltlllyl-N ()tfltttlotfylttlll[1101110) propzuiu-l-sullouatv 54. 5ll. Sodium tt-trapropylvue lit-uzt-no sull'ouale. 50. T

1 Based on cloth swatches.

It can be seen that the sultaine compounds of the present i vention, A &D exhibit superior lipid soil removing properti in cool water ascompared to the commonly used hot wat commercial detergent compounds,and in cool water a about equal to commercial detergent compounds usedin 14 F. The octadecyl homolog, while not as effective as t preferredhexadecyl compounds, is superior to SOClll. tetrapropylene benzenesulfonate in cool water.

Substantially the same performance advantages are c served by thehousewife when doing the home laundry water ranging from 40 to l00 F.,using conventior procedures. Woolens and synthetic fibers washed in thesame manner are cleaned as efficiently when washed according to theprocess ofthis invention and using the compositions ofthis invention asthey would be if they were washed in conventional detergent compositionsat hot water temperatures, yet a minimum of shrinkage and wrinklingtakes place and the feel of the wool is preserved to a greater extent.

While the compositions of this invention are outstandingly effective inwater at a temperature ranging from 40 F. to l F., the temperature rangein which the most outstanding results are seen is about 60 F. to 90 F.Below about 60 F. it has been found that the granular detergentcompositions of this invention are slow to dissolve. consequently, it ispreferred to use the liquid compositions at the lower temperatures.

The following compositions will illustrate the manner in which theproduct invention can be practiced. Included are both liquid andgranular formulations. it will be understood, however, that the examplesare not to be construed as limiting the scope of conditions claimedhereinafter. These composi tions are useful in automatic washers andconventional type washers as well as hand washing operations.

Solid:

B-(N,N-rlimcthyl-Ntctradocylannnonio)-2-hydroxypropanc-l-sulfonato.

'Ictrapotassinni pyrophosphatc.)

. Sodium silicate fNugOiSiOz=l2l0).

. Potassium tolucmsulfonatc.

Sodium carlmxy methyl hydroxy cthyl cellulose.

Water and minor amounts of misccllancous.

3-(N,N-dimcthyl-N-alkylamm0nio )-2-hydroxypropaiii-- l-sulfonatc.

Tetrapotassium pyrophosphonatc.

. Sodium silicate (NazO:SiO:=l:l.6).

. Potassium toluene sulfouatc.

. Sodium carboxy methyl ccllulosc.

Water.

3-(N,N-dimcthyl-N-alkylammoni0 )'2-hydroxypropancl-sulfonate.

Sodium tripolyphosphate.

. Sodium silicate (Nfl2OISiO:=1Z2.5).

Sodium tolucnc sulfonatc.

Sodium carboxy mcthyl cellulose.

Sodium sulfate.

. Fluorescent dyv.

Water.

Miscellaneous.

3-(N,N-dlmethyl-N-alkylammonio )-.2-hydroxypropanotd-sulfonate. l h t 60So ium yrop iosp a e. 6 2? Sodium silicate (NBzO2slOg=lI2.5). 2% Sodiumtoluene sulfonatc. 3%.. Sodium carboxy methyl cellulose. 11.3% H Water.Balancm Miscellaneous (fluoresccrs, perfume, anti-tarnish agents,

sodium sulfate, etc.).

3(N,N-dimethyl-N-alkylammonio )-2-hydroxypropanet-sulfonate.

Sodium tripolyphosphate.

Sodium silicate (N8:O.'SiOz=122.5).

Sodium tolutnio sulfonato.

Sodium carboxy methyl ccllulosc.

Sodium sulfate.

Water.

Miscellaneous.

3 (N,N-dimethyl-N-alky1ammon.io propane-l-sulfonatn. Sodiumtripolyphosphate. 6% Sodium silicate (Na2O:Si0:=1:2.5)v

till

.. Sodium caruoxy mvthyl t'vllulosv.

. odlum sulfatv.

. Watt-r.

. Mlsccllanoons.

1 Alkyl rt-ft-rring to tho it; group dcrivt-d front the middle cut oft'Ut'tlnut fatty alcohol (3) C t, till"; 2, 232'; Cu. '.l (I

Alkyl rt-ft-rriug to tho it. group ohtninvd from tallu fatty alcoholold"; (15. 30); Cu, 4"; Cu and others) 3 Alkyl referring to tln R grouptlll'iVt'tl front tlnmiddle (ill of coconut fatty alcohol (2Q 0. 66%(11. 23";- C 'J'I, (J 5).

It will be appreciated that the sultaine compounds used in the presentinvention can be incorporated into liquid or granular detergentcompositions with suitable adjustments being made in the othercomponents.

EXAMPLE Ill 1 Based on cloth swatches. Aver-ago of two tests. 3 Averageof three tests.

It can be seen from this data that detergent agents A, B, D, E, F, H, land J are superior in cool water detergency effectiveness to C and G.They are also markedly superior in cool water to K in hot water, K beingthe longtime standard organic detergent compound. The variation ineffectiveness within the preferred compounds can be seen in the aboveresults.

When, in detergent agents B and D in tetradecyl group is substituted forthe hexadecyl and dodecyl groups, respectively substantially equivalentresults are obtained in that the detergent agents are effective cleaningagents at F.

When, in the above example, mixtures of any and all of detergent agentsA, B, D, E, F, H, l and J, are substituted for any or all of detergentagents A, B, D, E, F, H, l or J, substantially equivalent results areobtained in that effective cool water cleaning is obtained.

Llt

LII

EXAMPLE IV Here a Cloth Swatch Test, previously described, was conductedunder the following conditions: water at a temperature of 80 F. or l40F. and 7 grains per gallon hardness, 0.03 percent detergent compound and0.06 percent sodium tripolyphosphate builder concentration in thewashing solution. (No fluorescers bleaches or antiredeposition agentswere used.) The detergent washing solution had a pH of 10. Seven cyclesofsoiling and cleaning were used.

LIPID REMOVAL BASED ON CLOTH SWA'lCHlzS Percent Removal Temper .llUYL'Detergent Agent A. Sodium coconntalkyl beta ainmonioummoniol-I-hydnnyprn ane-l-sulfonatc 44 II x I D. Sodium tetrapromlenebenzene Sulfonate 3x 5 I40 I As can be seen from the above table.detergent agent C is clearly superior to any of the other detergentagents but that detergent agent B is clearly superior to both detergentagents A and D. it will be noted that detergent agent A at 80 F. cannotapproach the performance ofdetergent agent D at 140 F. The performanceof detergent agent D at 140 F. is a standard criteria for adequatecleaning.

With reference to example 111. it will be noted that the detergentagents of this invention are all better in performance at 80 F. than theperformance ofdetergent agent D at 140 F.

When examples Ill and 1V pyrophosphates; ethylene diaminetetraacetates;N-(Z-hydroxyethyl)-ethylenediamine triacetates; nitrilo triacetates; N-(Z-hydroxyethyl nitrilodiacetates; phytates; methylenediphosphonates;ethylidene diphosphonates; isopropylidene diphosphonates;benzylmethylidene diphosphonates; chloromethylidene diphosphonates; andmixtures thereof in the form of their sodium potassium.triethanolammonium diethanolammonium, and monoethanolammonium salts andmixtures thereof are substituted, either wholly or in part. e.g.. a 50percent substitution, for the sodium tripolyphosphate buildersubstantially equivalent results are obtained in that for each buildersubstitution the detergent agents used in the process ofthis inventionare effective cleaning agents at temperatures of about 80 F. and theabove detergency building agents provide their buildingfunction withsuch agents. The surprising cool water superiority of these combinationsof such agents and builders is found on a relative basis throughout thecool water range of 60 F.-90 F.

Materials which are considered normal and desirable additives in liquidor granule detergent compositions can also be added to the compositionsof this invention without substantially modifying the basiccharacteristics of the sultaine detergent surfactants. For example atarnish inhibitor such as benzotriazole or ethylene thio-urea may beadded in amounts up to about lpercent. Fluorescers. perfume. colorantiredeposition agents, germicides, thickening agents opacifiers,blending or viscosity control agents, suds boosters and depressants andother detergent compounds, while not essential in the composition ofthis invention, can also be added.

All parts, percentages. and ratios herein are by weight unless otherwisespecified.

Since certain changes can be made in the process and composition withoutdeparting from the scope of the invention, it is intended that thedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:

l. The process of washing wash-wear fabrics in a washing solution havinga temperature of from about 60 F. to about F. and consisting essentiallyof A. from about 0.005 percent to about 0.175 percent of a/\\'itterionic quaternary ammonium compound selected from the groupconsisting of l 3-(N.N-dimethyl-N-alkylammonio) propane-l-sulfonateswherein the alkyl group contains from about 12 to about 16 carbon atoms;3-(N.N-dibutyl-N-alkylammonio) propane-lsulfonates wherein the alkylgroup contains about 12 carbon tttomS;

3. 3-(N.N-dimethyl-N-alkylammonio)-2-hydroxypropane-l-sulfonates whereinthe alkyl group contains from about 12 to about 16 carbon atoms;

4. 3-(N,N-diemthyl-N-alkylammonio)1,1.3-trimethylpropane-l-sulfonatewherein the alkyl group contains about 12 carbon atoms;

. 2-(N.N -dimethyl-N-coconutalkylammonio)ethane-lsulfonates;ethane-l-sulfonates; and

6. mixtures thereof;

B. from about 0.004 percent to about 0.45 percent of a detergencybuilder selected from the group consisting of pyrophosphates;

.ethylenediaminetetraacetates;

N-(2-hydroxyethyl)-ethylenediamine-triacetates;

nitrilotriacetates N-(Z-hydroxyethyl)-nitrilodiacetates;

. phytates;

. tripolyphosphates; and

. mixtures thereof in the form of their sodium, potassi' um;triethanolammonium. diethanolammonium, and monoethanol-ammonium saltsand mixtures thereof; and

C. water wherein the ratio of A to B by parts ranges from about 5:1 toabout 1:25 all percentages herein being by weight.

2. The process of claim I wherein Compound (A) is 3-(N,N-dimethy1-N-hexadecylamminio)propane-1-sulfonate.

3. The process of claim 1 wherein Compound (A) is 3(N,N-dimethyl-N-dodecylammonio)-2-hydroxypropane-l-sulfonate.

4. The process of claim wherein Compound (A) is 3-(N,N-dimethyl-N-coconutalkylammonio)-l-sulfonate.

5. The process of claim 1 wherein Compound (B) consists essentially oftripolyphosphates.

'" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,619,115 mud November 9, 1971 humor) Francis L. Diehl and Norman R.Smith It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

[Column 1, line 52, "waters" should read -water is--- Column 2 line 10,"nd" should read --and--.

Column 2 line 73, "3-(N,Nbibutyl-N-alkylammonio) propane-lsulfona tes"should read --3-(N,N-dimethylN-alkylammonio) propane-l-sulfonstes--.

Column 3, line 3, "3-(N,N-diemthyl-N-alkylanunonio)-2-hydroxypropanel-sulfonates" should read .3(N,N-dimethyl-N-alkylammonio) -2-hydroxypropane-l-sulEonates-.

Column 3, line 52, "3-(N,NdiemthylN-" should read --3-(N,N-

dimethyl-N-- Column 3, line 53, after "hydroxypropane-l" should read---sulfonate:--.

Column 3, line 53, "3-(N,N-diemthyl-N- should read --3-(N,N-

dimethylN- Column 3, line 54, "hydrosypropane" should read--hydroxypropane--.

Column 3, line 60, "3-N,N-dimethyl-N,N-tetradecylammonio) should read--3-(N,N-dimethyl-N-alkylammonio)-- Column 3, line 64, "tetradecylamino"should read --tetradecylammonio Column 3, line 66,"monio)butsnebutane-l-sulfonate: butane-lsulfonatm" should read--monio)butane-l-su1onate:-.

Column 3, line 68, (N-Z-hydroxyethyl-N-msthy) should read --(N-2-hydroxyethylN-methyl)--.

Column 4, line 26, "1'' should read --(1)--.

Column 4, line 29, the second "2" should read --(2) Column 4, line 30,"mg. should read --(e.g.

Column 4 line 31, the second "3" should read --(3)--.

Column 4, line 35, "4" should read --(4)--.

Column 4, line 37, "e.g. should read --(e.g.,--.

Column 4, line 42, "3,422,021: and 5 mixtures thereof" should read--3,422,021) and (5) mixtures thereot. J

m3" UNITED STATES PATENT omen CERTIFICATE OF CORRECTION a n 3,619,115 pNovember 9, i971 Inventor) Francis L. Diehl and Norman R. Smith It iscertified that error appears in the above-identified patent and thatsaid letters Patent are hereby corrected as shown below:

Page 2 Column 4, line 51, "sodium, silicate should read -sodium -1silicate-.

a Column 5, line 33, "is" should read --Tn--.

Column 5, line 34, "0.45" should read --.O45--. Column 6, line 6, "an"should read --and--. Column 7, line 2, "agltetingntype" should read--agitatingtype. Column 7, line 55, "sulbonate" should read--sulfonat'e--. Column 8, end or line 1, should read --1n--.

Column 8, end of line 2, should read --Ex---.

Column 8, end of line 3, should read --markedly--.

Column 8, end of line 4, should read --tetrapropylene--. Column 8, endof line ,6, should read was. Column 8, end of line 7, should read--detergent-. :olumn 8, end of line 8, should read --com---'.

Zolumn 8, end of line 9, should read -:-de--.

201mm 8, end of line 10, should read --waeh1ng--.

:olumn 8, end of line ll, should read --and--.

tolumn 8, end or line 12, should read --luoresoers,--. :olumn 8, end ofline 13, should read --washing--.

.olumn 8, end or line 14 or 15, should read --ga1lon--. olumn 8, end ofline 16, should read --3---.

rolumn 8, end of line 17, should read 3---.

olumn 8, end or line 19, should read --inventlon) olumn 8, end of line20, should read --benzene--.

olumn 8, end or line 21, should read --con---.

olumn 8, end of line 22, should read --N---.

olumn 8, end of line 23, should read --N---.

olumn 8, end or line 25, should read --deter---.

olumn 8, end of line 26, should read --80'F.--.

olumn 8, end of line 27, should read --was--.

PO-IOSO Patent No.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated Francis L.Diehl and Norman R. Smith and that said Letters Patent are C olumnColunm Column Column Column Column Column Column Column Column ColumnColumn Column Column Column Column Column Column Column Column ColumnColumn Column Column Column Column Column Column Colunm ll, line 14,

end end end end end end end end end end end end end end end end end endend end end end end end end of of of of of of of of of of of of of of ofof of of or of of of of of 11, line Column ll, line Eolumn 11, line 2e,29, so, 31, 32, 34, as, as, 37, 42, 43,

line line line line line line line 71, line 73, line' 74, line 75,

as, 66, e7, 68, 69, 10,

Page

read read read the above-identified patent herebg corrected as shownbelow:

--tal---. -sulfonate-. --is--.

--dt-" s --sultaine--. --White-. --builder-. --potassium--.--tripolyphosphate.--. --o.os--. --the--.

-Temperature, F.- --80--.

& 55, should read --l40-. lines 56-60, should read --80-.

read read read read read read read read read read should should shouldshould should should should should should should line 53,"pyrophosphate.)" line 59, the second "in" should read should readshould read should read --ln---. --properties-. --water--.

--are--. --l40'--. --the-. --sodium--. --ob---.

--in--. --conventional--.

should read --pyrophosphate should read --a-.

'" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION mm No.3,619,115 mm November 9,1911

Inmgr(.) Francis L. Diohl and Norman R. Smith It in cottiiiod that ortotoppooro in tho obovo-idontitiod potoot and that aid Lotta-o Paton: nohoroby ootrootod no shown bolov:

Pogo 4 olumn 12, lino 24,"3-(N,N-diomthyl-N-olkylamonio)1,1,3-trimethblohould road--3-(N,N-dimothyl-N-olkylomonio)-l,l,3-trimothyl- Column 12, lino 25,propono-l-oultonoto" should read --propaneloulfonatoo--. Column 12, lino28, tho oooond "othono-l-oulfonatoa ohould be dolotod. Column 12, lino47, (N,N-dimothyl-N-hoxodocylominio) should road--(N,N-dimothyl-N-hoxodooylamaonio)--. column 12, lino 53, alto: "claim"and botoro "whoroin" ohould road --l--. column 12, lino 54,"dimothyl-R-coconutolkyloumonio)-l-oulfonate" ohould road--dimothyl-fl-coconutolkylomaonio) -2-hydroxypropanel-ou1onoto-.

Signod and ooolod thio 13th on] 0! ul! 97 (SEAL) Attoot:

EDHARD HJLBTOHKRJR. ROBERT OO'I'I'SOHAIK Attooting crum- Oomiooionor orPotonto

2. 3-(N,N-dibutyl-N-alkylammonio) propane-1sulfonates wherein the alkylgroup contains about 12 carbon atoms;
 2. The process of claim 1 whereinCompound (A) is 3-(N,N-dimethyl-N-hexadecylamminio)propane-1-sulfonate.2. ethylenediaminetetraacetates;
 3. The process of claim 1 whereinCompound (A) is3(N,N-dimethyl-N-dodecylammonio)-2-hydroxypropane-1-sulfonate. 3.3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonates whereinthe alkyl group contains from about 12 to about 16 carbon atoms; 3.N-(2-hydroxyethyl)-ethylenediamine-triacetates;
 4. nitrilotriacetates,4. 3-(N,N-diemthyl-N-alkylammonio)1,1,3-trimethylpropane-1-sulfonatewherein the alkyl group contains about 12 carbon atoms;
 4. The processof claim wherein Compound (A) is3-(N,N-dimethyl-N-coconutalkylammonio)-1-sulfonate.
 5. The process ofclaim 1 wherein Compound (B) consists essentially of tripolyPhosphates.5. 2-(N,N,-dimethyl-N-coconutalkylammonio)-ethane-1-sulfonates;ethane-1-sulfonates; and
 5. N-(2-hydroxyethyl)-nitrilodiacetates; 6.phytates;
 6. mixtures thereof; B. from about 0.004 percent to about 0.45percent of a detergency builder selected from the group consisting of 7.tripolyphosphates; and
 8. mixtures thereof in the form of their sodium,potassium, triethanolammonium, diethanolammonium, andmonoethanol-ammonium salts and mixtures thereof; and C. water, whereinthe ratio of A to B by parts, ranges from about 5:1 to about 1:25 , allpercentages herein being by weight.